CA1125449A - Polyolefin articles sterilisable by gamma-irradiation - Google Patents
Polyolefin articles sterilisable by gamma-irradiationInfo
- Publication number
- CA1125449A CA1125449A CA332,558A CA332558A CA1125449A CA 1125449 A CA1125449 A CA 1125449A CA 332558 A CA332558 A CA 332558A CA 1125449 A CA1125449 A CA 1125449A
- Authority
- CA
- Canada
- Prior art keywords
- article
- hindered amine
- irradiation
- amine
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/143—Stabilizers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
Abstract
ABSTRACT OF THE DISCLOSURE
Polyolefin articles, especially polypropylene hypodermic syringes are made more resistant to the yellow discolouration and embrittlement which accompanies sterilisation by gamma-irradiation by the addition to the polyolefin of a heterocyclic hindered amine.
Polyolefin articles, especially polypropylene hypodermic syringes are made more resistant to the yellow discolouration and embrittlement which accompanies sterilisation by gamma-irradiation by the addition to the polyolefin of a heterocyclic hindered amine.
Description
~lZ~ g POLYOLEFIN ARTICLES STERILISABLE BY GAM~-IRRADIATION
This invention relates to polyolefin articles, especially polypropylene hypodermic syringe components which are suitable for sterilisation by gamma-irradiation from a cobalt-60 source.
Polypropylene syringes have been in use for many years (see British patent specification 1 050 802 published in 1966) and have been sterilised by gamma-irradiation even though this causes yellow discolouration and/or embrittlement of the syringe. Plester reports (see "Bio-Medical Engineering" September 1970, pages 443 to 447) that polypropylene is of only "borderline"
suitability for such use and accordingly many attempts have been made to alleviate the problem. Nevertheless, the problem has persisted and was discussed and left unsolved by Williams et al in "Radiation Physics and Chemistry", Volume 9, pages 445 to 454, published in 1977.
It has now been discovered that polyolefins containing certain hindered amines are more resistant to the discolouration which occurs as a result of gamma-irradiation. Typical hindered amines are described in West German patent specifications 2 204 659 and 2 319 816, published in 1972 and 1973 respectively.
Accordingly, this invention provides an article of medical (including hospital) ware sterilisable by gamma-irradiation from a cobalt-60 source and made from a composition comprising a crystalline polymer of an aliphatic alpha-olefin characterised in that the composition comprises from 0.01 to 2 (preferably 0.08 to 0.3)% by weight of the polymer of a hindered amine or its salt, N-oxide, N-hydroxide or N-nitroxide wherein the amine nitrogen is contained in a carbon-nitrogen-carbon chain which forms part of a non-aromatic heterocyclic ring and wherein each of the two carbon atoms of the chain is bonded to two same or different lower alkyl groups each ll~Z~ 9
This invention relates to polyolefin articles, especially polypropylene hypodermic syringe components which are suitable for sterilisation by gamma-irradiation from a cobalt-60 source.
Polypropylene syringes have been in use for many years (see British patent specification 1 050 802 published in 1966) and have been sterilised by gamma-irradiation even though this causes yellow discolouration and/or embrittlement of the syringe. Plester reports (see "Bio-Medical Engineering" September 1970, pages 443 to 447) that polypropylene is of only "borderline"
suitability for such use and accordingly many attempts have been made to alleviate the problem. Nevertheless, the problem has persisted and was discussed and left unsolved by Williams et al in "Radiation Physics and Chemistry", Volume 9, pages 445 to 454, published in 1977.
It has now been discovered that polyolefins containing certain hindered amines are more resistant to the discolouration which occurs as a result of gamma-irradiation. Typical hindered amines are described in West German patent specifications 2 204 659 and 2 319 816, published in 1972 and 1973 respectively.
Accordingly, this invention provides an article of medical (including hospital) ware sterilisable by gamma-irradiation from a cobalt-60 source and made from a composition comprising a crystalline polymer of an aliphatic alpha-olefin characterised in that the composition comprises from 0.01 to 2 (preferably 0.08 to 0.3)% by weight of the polymer of a hindered amine or its salt, N-oxide, N-hydroxide or N-nitroxide wherein the amine nitrogen is contained in a carbon-nitrogen-carbon chain which forms part of a non-aromatic heterocyclic ring and wherein each of the two carbon atoms of the chain is bonded to two same or different lower alkyl groups each ll~Z~ 9
- 2 - 30341 c:ontaining 1 to 12 carbon atoms or to an alicyclic group c:ontaining 4 to 9 carbon atoms which groups sterically hinder the amine. In general, the articles can receive a radiation dose of 5.0 Mrad from a cobalt-60 source and then have a discolouration factor (as hereinafter defined) of better than 0.750 (often better than 0.800) two weeks after irradiation and an oven life in air at 150C of at least 6 and often over 10 days in sections 3.17 mm thick.
The hindered amines preferably comprise a 5- or 6-memhered heterocyclic ring containing the hindered amine nitrogen and optionally another hetero atom preferably nitrogen or oxygen. If the hindered amine is a tertiary amine, the tertiary group may be, for example, an optionally substituted alkyl, aralkyl, alkaryl or alicyclic group containing 1 to 12 carbon atoms and one or more of the substituents may be hindered amines so that the tertiary group may be used to link a plurality of hindered amines. m e hindering groups are preferably alkyl groups containing 1 to 4 carbon atoms and most preferably all four groups are methyl. The most preferred hindered amines comprise 2,2,4,4-tetramethyl piperidine derivatives.
The hindered amine is preferably bonded to a carrier moiety which should have little if any inhibiting effect on the chemical activity of the hindered amine.
Reasonably inert carriers include aromatic compounds ~for example those based on the benzene, imidazole or triazine rings), saturated hydrocarbon compounds, esters or amides of carboxylic acids, ketones and ether, thioether, sulphinyl or sulphone groups. Preferably, in order to reduce the extractability of the hindered amines from polyolefins, the carriers can be used to link together a plurality of hindered amines and hence the tertiary groups may be regarded as carriers too.
Examples of hindered amines linked by diesters or ketones include:
1~2~449
The hindered amines preferably comprise a 5- or 6-memhered heterocyclic ring containing the hindered amine nitrogen and optionally another hetero atom preferably nitrogen or oxygen. If the hindered amine is a tertiary amine, the tertiary group may be, for example, an optionally substituted alkyl, aralkyl, alkaryl or alicyclic group containing 1 to 12 carbon atoms and one or more of the substituents may be hindered amines so that the tertiary group may be used to link a plurality of hindered amines. m e hindering groups are preferably alkyl groups containing 1 to 4 carbon atoms and most preferably all four groups are methyl. The most preferred hindered amines comprise 2,2,4,4-tetramethyl piperidine derivatives.
The hindered amine is preferably bonded to a carrier moiety which should have little if any inhibiting effect on the chemical activity of the hindered amine.
Reasonably inert carriers include aromatic compounds ~for example those based on the benzene, imidazole or triazine rings), saturated hydrocarbon compounds, esters or amides of carboxylic acids, ketones and ether, thioether, sulphinyl or sulphone groups. Preferably, in order to reduce the extractability of the hindered amines from polyolefins, the carriers can be used to link together a plurality of hindered amines and hence the tertiary groups may be regarded as carriers too.
Examples of hindered amines linked by diesters or ketones include:
1~2~449
- 3 - 30341 a) di-(2,2,6,6~tetramethyl-4-piperidyl) sebacate (see formula I) where it is the sebacate which is the carrier, b) di-(2,2,6,6-tetramethyl-4-piperidyl) 1-~3,5-ditertiarybutyl-4-hydroxyphenylmethyl)-1,1-pentanedicarboxylate (see formula II) where it is the pentanedicarboxylate which is the carrier, c) the condensate of succinic acid and N-(2-hydroxypropyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine (see formula III) where both the succinate moiety and the tertiary propoxy groups combine to form carriers, The condensate preferably contains 6 to 20 hindered amine groups, and d) 1,4-di-(2,2,6,6-tetramethyl-4-piperidyl)-2,3-butanedione (see formula IV) where it is the butanedione which is the carrier.
The polyolefin can be, for example, a homopolymer of ethylene (low or high density polyethylene), propylene, butene-l or 4-methyl-pentene-1 or a copolymer of two or more of these monomers. Preferred copolymers are copolymers of propylene and either from 7 to 20% (by weight of the copolymer) of ethylene when made by injecting ethylene into the latter stages of an otherwise homopolymerisation of propylene or from 0.5 to 10% of ethylene when made by random copolymerisation. Copolymers of ethylene with up to 30% of vinyl acetate, methyl, ethyl or butyl (including tertiary butyl) acrylates or methacrylates or acrylic or methacrylic acids may also be used. Preferably, the polyolefins have melt flow indexes of from 0.1 to 25 g/10 minutes when measured according to British Standard 2782 Part 1/105C of 1970 using a 2.16 kg load at 230C in the case of polymers containing a major amount of polymerised propylene and at l9QC in all other cases. Added rubbers improve impact strength.
~ZS449 ~ 4 ~ 30341 The composition may contain stabilising amounts (e.g.
0.01 to 2% by weight of the polymer) of light stablisers (e.g. benzotriazoles) and~or phenolic antioxidants of the kind used in polyolefins, for example, n-octadecyl 3-(3,5-ditertiarybutyl-4-hydroxyphenyl) propionate. However, phenolic antioxidants may aggravate discolouration so their use may entail sacrifice of some of the improvement in discolouration. The compositions may also contain stabilising amounts of sulphur compounds of the type known to synergise with phenolic antioxidants in polyolefins, for example, long chain (e.g. ~10 to C22) mercap and sulphides but the preferred compounds are dialkyl thiodialkanoates especially when the alkyl groups contain from 10 to 22 carbon atoms and the alkanoic acids contain from 2 to 6 carbon atoms. Specific examples are dilauryl and distearyl thiodipropionate. The compositions preferably contain from 0.01 to 10% (usually 0.1 to 0.5%) by weight of organic sulphur compound. Other conventional additives such as pigments or moulding aids may be used.
Articles of sterilisable medical ware according to this invention include syringe components (such as barrels, plungers and needle hubs), catheters, cannulae and prosthetic devices and also wrappings for such articles.
The invention is illustrated by the following examples of which A to I are comparative.
EXAMPLES A TO I AND 1 to 3 Using a high speed powder mixer, powdered propylene homopolymer having a melt flow index of 8 g/10 minutes was mixed with 0.2% by weight of powdered calcium stearate and various amounts of various powdered additives as specified in Table 1. (The percentages specified in Table 1 and of calcium stearate are based on the weight of the polymer).
Each mixture of powders was heated to 225C to melt the polymer and the melt was converted to granules. Each l~lZ~
batch of granules was injection moulded into discs 3.17 mm thick and 11.4 cm in diameter.
Sample discs were retained as controls and the rest were irradiated at 2.5 or 5.0 Mrad using a cobalt-60 source. The irradiated discs were divided into three groups. The first group were kept under ambient conditions for 2 weeks and then their discolouration factors were measured. They were then kept under ambient conditions for a period of three months after irradiation and then their discolouration factors were measured again.
The second group of discs were kept under ambient conditions for 4 weeks and then placed in an air-circulating oven maintained at 100C for three days. On removal from the oven and cooling to ambient temperature, the discolouration factors of the discs were measured.
The third group of discs were put into an air-circulating oven maintained at 150C and the time taken for them to embrittle (i.e. for surface cracking to appear) was noted. All the results are shown in Table 2.
"Discolouration factor" is measured using a 'Colormaster' differential colorimeter as supplied by the Manufacturers, Engineering and Equipment Corporation of Warrington, Pennsylvania/ USA.
A beam of blue light from the 'Colormaster' was shone onto a white surface at an angle of incidence af q5~ so as to illuminate an area of the surface. The intensity of light leaving the illuminated area in a direction normal to the surface was registered by the 'Colormaster'. A
disc 3.17 mm thic~ was then placed over the illuminated area and was compared by the 'Colormaster'. The procedure was repeated using red light and the ratio of loss of intensity of blue light to loss of intensity of red light as compared by the 'Colormaster' was calculated. This ratio is defined as the "discolouration factor".
~25449 The higher the discolouration factor, the lower is the yellow discolouration of the sample. Therefore, it will be seen that in general the least yellow discolouration occurred in Examples 1, 2, 3 and A, but in the case of A, the brittleness of the sample was unacceptable.
Example % by weight % by weight % by weight antioxidant thioester other *additive B _ 0.3 _ C 0.1 0.3 D 0.2 0.5 E 0.1 0.3 0.3a F 0.1 0.3 O.lb G 0.1 0.3 O.lc H 0 1 0.3 O.ld .
I Proprietry Composition _ _ 1 0 1 _ 0 2e 3 0.1 _ 0.2g *Additives a = di-benzylidene sorbitol.
b = a mixture of tri-mono and tri-di-nonyl phenyl phosphite containing 1% by weight (of the weight of the phosphite) o~ tri-isopropanol amine.
c = tris-(2,4-ditertiary butyl phenyl) phosphite.
d = a proprietry organic phosphonite.
e = as formula III.
f = as formula II.
g = as formula I.
.
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The polyolefin can be, for example, a homopolymer of ethylene (low or high density polyethylene), propylene, butene-l or 4-methyl-pentene-1 or a copolymer of two or more of these monomers. Preferred copolymers are copolymers of propylene and either from 7 to 20% (by weight of the copolymer) of ethylene when made by injecting ethylene into the latter stages of an otherwise homopolymerisation of propylene or from 0.5 to 10% of ethylene when made by random copolymerisation. Copolymers of ethylene with up to 30% of vinyl acetate, methyl, ethyl or butyl (including tertiary butyl) acrylates or methacrylates or acrylic or methacrylic acids may also be used. Preferably, the polyolefins have melt flow indexes of from 0.1 to 25 g/10 minutes when measured according to British Standard 2782 Part 1/105C of 1970 using a 2.16 kg load at 230C in the case of polymers containing a major amount of polymerised propylene and at l9QC in all other cases. Added rubbers improve impact strength.
~ZS449 ~ 4 ~ 30341 The composition may contain stabilising amounts (e.g.
0.01 to 2% by weight of the polymer) of light stablisers (e.g. benzotriazoles) and~or phenolic antioxidants of the kind used in polyolefins, for example, n-octadecyl 3-(3,5-ditertiarybutyl-4-hydroxyphenyl) propionate. However, phenolic antioxidants may aggravate discolouration so their use may entail sacrifice of some of the improvement in discolouration. The compositions may also contain stabilising amounts of sulphur compounds of the type known to synergise with phenolic antioxidants in polyolefins, for example, long chain (e.g. ~10 to C22) mercap and sulphides but the preferred compounds are dialkyl thiodialkanoates especially when the alkyl groups contain from 10 to 22 carbon atoms and the alkanoic acids contain from 2 to 6 carbon atoms. Specific examples are dilauryl and distearyl thiodipropionate. The compositions preferably contain from 0.01 to 10% (usually 0.1 to 0.5%) by weight of organic sulphur compound. Other conventional additives such as pigments or moulding aids may be used.
Articles of sterilisable medical ware according to this invention include syringe components (such as barrels, plungers and needle hubs), catheters, cannulae and prosthetic devices and also wrappings for such articles.
The invention is illustrated by the following examples of which A to I are comparative.
EXAMPLES A TO I AND 1 to 3 Using a high speed powder mixer, powdered propylene homopolymer having a melt flow index of 8 g/10 minutes was mixed with 0.2% by weight of powdered calcium stearate and various amounts of various powdered additives as specified in Table 1. (The percentages specified in Table 1 and of calcium stearate are based on the weight of the polymer).
Each mixture of powders was heated to 225C to melt the polymer and the melt was converted to granules. Each l~lZ~
batch of granules was injection moulded into discs 3.17 mm thick and 11.4 cm in diameter.
Sample discs were retained as controls and the rest were irradiated at 2.5 or 5.0 Mrad using a cobalt-60 source. The irradiated discs were divided into three groups. The first group were kept under ambient conditions for 2 weeks and then their discolouration factors were measured. They were then kept under ambient conditions for a period of three months after irradiation and then their discolouration factors were measured again.
The second group of discs were kept under ambient conditions for 4 weeks and then placed in an air-circulating oven maintained at 100C for three days. On removal from the oven and cooling to ambient temperature, the discolouration factors of the discs were measured.
The third group of discs were put into an air-circulating oven maintained at 150C and the time taken for them to embrittle (i.e. for surface cracking to appear) was noted. All the results are shown in Table 2.
"Discolouration factor" is measured using a 'Colormaster' differential colorimeter as supplied by the Manufacturers, Engineering and Equipment Corporation of Warrington, Pennsylvania/ USA.
A beam of blue light from the 'Colormaster' was shone onto a white surface at an angle of incidence af q5~ so as to illuminate an area of the surface. The intensity of light leaving the illuminated area in a direction normal to the surface was registered by the 'Colormaster'. A
disc 3.17 mm thic~ was then placed over the illuminated area and was compared by the 'Colormaster'. The procedure was repeated using red light and the ratio of loss of intensity of blue light to loss of intensity of red light as compared by the 'Colormaster' was calculated. This ratio is defined as the "discolouration factor".
~25449 The higher the discolouration factor, the lower is the yellow discolouration of the sample. Therefore, it will be seen that in general the least yellow discolouration occurred in Examples 1, 2, 3 and A, but in the case of A, the brittleness of the sample was unacceptable.
Example % by weight % by weight % by weight antioxidant thioester other *additive B _ 0.3 _ C 0.1 0.3 D 0.2 0.5 E 0.1 0.3 0.3a F 0.1 0.3 O.lb G 0.1 0.3 O.lc H 0 1 0.3 O.ld .
I Proprietry Composition _ _ 1 0 1 _ 0 2e 3 0.1 _ 0.2g *Additives a = di-benzylidene sorbitol.
b = a mixture of tri-mono and tri-di-nonyl phenyl phosphite containing 1% by weight (of the weight of the phosphite) o~ tri-isopropanol amine.
c = tris-(2,4-ditertiary butyl phenyl) phosphite.
d = a proprietry organic phosphonite.
e = as formula III.
f = as formula II.
g = as formula I.
.
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Claims (6)
1. An article of medical ware sterilisable by gamma-irradiation from a cobalt-60 source and made from a composition comprising a crystalline polymer of an aliphatic alpha-olefin wherein the composition comprises from 0.01 to 2% by weight of the polymer of a hindered amine or its salt, N-oxide, N-hydroxide or N-nitroxide wherein the amine nitrogen is contained in a carbon-nitrogen-carbon chain which forms part of a non-aromatic heterocyclic ring and wherein each of the two carbon atoms of the chain is bonded to two same or different lower alkyl groups each containing 1 to 12 carbon atoms or to an alicyclic group containing 4 to 9 carbon atoms which groups sterically hinder the amine.
2. An article as claimed in claim 1 wherein the hindered amine comprises a 6-membered heterocyclic ring.
3. An article as claimed in claim 2 wherein the hindered amine is carried by a carrier comprising a dicarboxylate.
4. An article as claimed in claim 2 wherein the hindered amine is carried by a carrier comprising a triazine ring.
5. An article as claimed in claim 2 wherein the hindered amine is carried by a carrier comprising a diketone.
6. An article as claimed in Claim 1, 2 or 3 wherein the article is a component for a hypodermic syringe.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7831086 | 1978-07-25 | ||
| GB31086/78 | 1978-07-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1125449A true CA1125449A (en) | 1982-06-08 |
Family
ID=10498655
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA332,558A Expired CA1125449A (en) | 1978-07-25 | 1979-07-25 | Polyolefin articles sterilisable by gamma-irradiation |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0007736B1 (en) |
| JP (1) | JPS6029501B2 (en) |
| AT (1) | ATE4992T1 (en) |
| AU (1) | AU528404B2 (en) |
| CA (1) | CA1125449A (en) |
| DE (1) | DE2966294D1 (en) |
| DK (1) | DK301979A (en) |
| IE (1) | IE48527B1 (en) |
| NZ (1) | NZ191075A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5417969A (en) * | 1991-09-20 | 1995-05-23 | Baxter International Inc. | Process for reducing the thrombogenicity of biomaterials |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57179234A (en) * | 1981-04-28 | 1982-11-04 | Nippon Chibagaigii Kk | Radiation resistant polyolefin composition |
| FR2512453B1 (en) * | 1981-09-07 | 1988-07-29 | Toa Nenryo Kogyo Kk | POLYOLEFINIC COMPOSITION HAVING IMPROVED RESISTANCE TO RADIATION AND ITS USE FOR MEDICAL INSTRUMENTS |
| JPS5842638A (en) * | 1981-09-07 | 1983-03-12 | Toa Nenryo Kogyo Kk | Polypropylene composition having improved radiation resistance |
| JPS5849737A (en) * | 1981-09-19 | 1983-03-24 | Mitsubishi Petrochem Co Ltd | Polyolefin composition with resistance to gamma ray irradiation |
| EP0078603A1 (en) * | 1981-10-12 | 1983-05-11 | Imperial Chemical Industries Plc | Polyolefin compositions and articles sterilisable by irradiation |
| CA1207481A (en) * | 1982-02-23 | 1986-07-08 | Joel L. Williams | Radiation stabilization of polymeric material |
| US4507415A (en) * | 1982-03-27 | 1985-03-26 | Terumo Kabushiki Kaisha | Medical articles |
| EP0155912A3 (en) * | 1984-03-20 | 1986-06-04 | Ciba-Geigy Ag | Radiation-stabilized polymer compositions |
| US4888369A (en) * | 1987-01-21 | 1989-12-19 | Himont Incorporated | Polypropylene composition resistant to high energy radiation, and radiation sterilized articles therefrom |
| US4797438A (en) * | 1987-05-11 | 1989-01-10 | The B. F. Goodrich Company | Stabilized gamma-irradiated polypropylene and sterilizable articles thereof |
| JPH0663119U (en) * | 1991-06-21 | 1994-09-06 | 株式会社アイディ | Sheet-shaped adsorbent |
| FI94138C (en) * | 1992-01-10 | 1995-07-25 | Borealis Holding As | Polymer composition comprising sterilization by radiation and process for its preparation |
| EP0735089B1 (en) * | 1995-03-31 | 2004-09-22 | Basell North America Inc. | Polyolefin compositions resistant to high energy radiation, and articles produced therefrom |
| CN106751158B (en) * | 2016-12-01 | 2019-05-28 | 北京化工大学 | A kind of radiation resistance high molecular material and its preparation method and application |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3537967A (en) * | 1966-07-29 | 1970-11-03 | Dart Ind Inc | Radiation sterilized,thiodipropionic acid ester stabilized,propylene polymers |
| US3640928A (en) * | 1968-06-12 | 1972-02-08 | Sankyo Co | Stabilization of synthetic polymers |
| US3758273A (en) * | 1970-04-03 | 1973-09-11 | Gillette Co | Processes for sterilizing polypropylene objects |
| BE792043A (en) * | 1971-11-30 | 1973-05-29 | Ciba Geigy | PIPERIDINE DERIVATIVES USED TO STABILIZE ORGANIC MATERIALS |
| DE2661090C2 (en) * | 1975-11-07 | 1990-02-08 | Ciba-Geigy Ag, Basel, Ch | |
| CH597298A5 (en) * | 1975-11-07 | 1978-03-31 | Ciba Geigy Ag | (4)-Piperidyl hydroxybenzyl-malonates and -malonamides |
| CH597297A5 (en) * | 1975-11-07 | 1978-03-31 | Ciba Geigy Ag | (4)-Piperidyl hydroxybenzyl-malonates and -malonamides |
| CH626109A5 (en) * | 1976-05-11 | 1981-10-30 | Ciba Geigy Ag |
-
1979
- 1979-07-10 DE DE7979301347T patent/DE2966294D1/en not_active Expired
- 1979-07-10 AT AT79301347T patent/ATE4992T1/en active
- 1979-07-10 EP EP79301347A patent/EP0007736B1/en not_active Expired
- 1979-07-18 DK DK301979A patent/DK301979A/en not_active Application Discontinuation
- 1979-07-20 NZ NZ191075A patent/NZ191075A/en unknown
- 1979-07-23 AU AU49130/79A patent/AU528404B2/en not_active Ceased
- 1979-07-25 CA CA332,558A patent/CA1125449A/en not_active Expired
- 1979-07-25 JP JP54094845A patent/JPS6029501B2/en not_active Expired
- 1979-08-08 IE IE1326/79A patent/IE48527B1/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5417969A (en) * | 1991-09-20 | 1995-05-23 | Baxter International Inc. | Process for reducing the thrombogenicity of biomaterials |
Also Published As
| Publication number | Publication date |
|---|---|
| AU528404B2 (en) | 1983-04-28 |
| IE48527B1 (en) | 1985-02-20 |
| DE2966294D1 (en) | 1983-11-17 |
| JPS5519199A (en) | 1980-02-09 |
| AU4913079A (en) | 1980-01-31 |
| ATE4992T1 (en) | 1983-10-15 |
| DK301979A (en) | 1980-01-26 |
| IE791326L (en) | 1980-01-25 |
| EP0007736B1 (en) | 1983-10-12 |
| JPS6029501B2 (en) | 1985-07-11 |
| NZ191075A (en) | 1981-12-15 |
| EP0007736A1 (en) | 1980-02-06 |
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